Poly(vinyl acetate-dialkyl maleate-acrylic acid)textile sizes

ABSTRACT

COMPOSITIONS FOR SIZING TEXTILE YARNS COMPRISING A SOLUTION OF AN INTERPOLYMERIZATION PRODUCT OF VINYL ACETATE DIALKYL MALEATE AND ACRYLIC ACID IN AN AQUEOUS BASE.

nitedStates Patent 01 fee 3,817,892 Patented June 18, 1974 US. Cl. 26029.6 TA 7 Claims ABSTRACT OF THE DISCLOSURE Compositions for sizing textile yarns comprising a solution of an interpolymerization product of vinyl acetate dialkyl maleate and acrylic acid in an aqueous base.

CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of application Ser. No. 98,915, filed Dec. 16, 1970, now US. Pat. No. 3,723,381, granted Mar. 27, 1973.

- BACKGROUND OF THE INVENTION 1. Field of the invention The present invention relates to textile sizes. More particularly, it relates to poly(vinyl acetate-dialkyl 'maleate-acrylic acid) textile sizes wherein the dialkyl maleate is selected from the group consisting of dimethyl maleate and diethyl maleate and to textiles sized with these materials.

2. The prior art Polymeric substances are well known in the prior art for use as textile sizes. In conventional loom operations yarn is sized with an aqueous solution of a water soluble material such as a copolymer of vinyl acetate and carboxylic acid, woven into cloth on a conventional loom with a mechanical shuttle and then the size is removed in a water bath. While these sizes have been adequate in the past, recent developments in the textile industry have created an increasing demand for textile sizes with improved tensile strength, elongation, toughness, solubility characteristics, etc.

One such development in recent years is the water jet loom. The water jet loom employs a jet of water in place of a mechanical shuttle in order to weave the yarn into a fabric A water jet loom provides a faster weaving operation and less mechanical abrasion of the yarn. The result is an increase in production and improved quality in the woven fabric.

The size used in water jet weaving operations is customarily applied from aqueous solution. Once it is applied to the yarn and dried, the size must be sufficiently water resistant so as to remain on the yarn during the weaving operation. Moreover, in order to be efiicient and effective, the size must retain its adhesion and film properties such as high tensile strength when wet by the water jets in the weaving process without become soft and slimy. Finally, the size must be soluble in mild aqueous alkali solutions or organic solvents so that it can be removed from the woven fabric. The foregoing properties are the results of a critical inter-relationship between chemical composition and molecular weight of the polymeric material which is used as the textile size.

The sizes of the prior art which are customarily used in conventional loom weaving operations are found to lack the necessary physical properties which are required for use with water jet looms.

Thus, there exists in the art a need for improved textile sizes which can be used to size yarns which are to be woven on conventional or water jet looms and then removed using either an aqueous alkali solution or an organic solvent.

SUMMARY OF THE INVENTION The above-mentioned need in the prior art is fulfilled by the present invention which provides poly(vinyl acetate-dialkyl maleate-acrylic acid) textile sizes which are suitable for use on both conventional and water jet looms.

The textile sizes of the present invention have excellent solubility characteristics and film properties. Moreover, these sizes are easily removed from sized yarns or the resulting fabric using aqueous alkali solutions or organic solvents. Consequently, these sizes are especially suitable for use as yarn warp sizes for use on conventional or water jet looms.

THE PREFERRED EMBODIMENTS The sizes of the present invention are prepared from latices obtained by interpolymerizing vinyl acetate, a dialkyl maleate selected from the group consisting of dimethyl maleate and diethyl maleate and acrylic acid. The polymerization charge comprises from 83 to by weight of vinyl acetate, from 2 to 10% by weight of dialkyl maleate and from 3 to 7% by weight of acrylic acid based on the total weight of the monomers. More preferably, the polymerization charge comprises from 87.5 to 91% by weight of vinyl acetate, from 5 to 7.5% by weight of dialkyl maleate and from 4 to 6% by weight of acrylic acid based on the total weight of the monomers.

The monomers are polymerized using latex polymerization methods at a temperature in the range of from 40 to 60 C. and preferably at a temperature in the range of from 40 to 45 C. At temperatures below about 40 C. the polymerization rate is too slow and the reaction mass tends to coagulate. At polymerization temperatures above 60 C. the product is of low molecular weight and lacks the tensile strength and elongation required in sizes for use on water jet looms.

The interpolymerization is carried out using a surfactant which comprises an anionic phosphate ester of an alkyl phenol-ethylene oxide condensate wherein the alkyl group contains from 7 to 11 carbon atoms. Especially preferred are the phosphate esters of tertiary octyl phenol-ethylene oxide condensates (hereinafter referred to as PEOPEO) and the phosphate esters of nonyl phenol-ethylene oxide condensates (PENPEO). These preferred surfactants are available commercially as Triton XQS (Rhom & Haas Company) and GAFAC RE-870 (General Aniline & Film Company), respectively. The amount of the phosphate ester of an alkyl phenolethylene oxide condensate used will be in the range of from 1.0 to 4.0% by weight based on the total weight of the latex.

Preferably, the interpolymerization of the monomers is carried out using an anionic co-surfactant in combination with the phosphate esters of an alkyl phenol-ethylene oxide condensate. The use of the co-surfactants reduces the amount of coagulum in the resulting latex and provides a better product. The preferred co-surfactants used in the present invention includes alkyl sulfonates such as sodium dodecyl benzene sulfonate; fatty alcohol sulfates such as sodium lauryl sulfate; dialkyl sulfosuccinates, sodium dihexyl sulfosuccinate; etc.

The amount of co-surfactant used is in the range of 0.1 to 0.3% by weight and more preferably 0.15 to 0.25% by weight based on the total weight of the latex.

The polymerization processes are initiated by a two component redox free radical initiator system. Suitable oxidizing components for the system are the inorganic peracid salts such as ammonium, potassium and sodium 3 4 persulfates, perborates, and hydrogen peroxide. Preferred, The PEOPEO surfactant, ammonium hydroxide buffer however, are the oil soluble organic hydroperoxides such solution, sodium formaldehyde sulfoxylate and the water as t-butyl hydroperoxide, cumene hydroperoxide, p-menare charged to a glass lined reaction vessel. The tertiary thane hydroperoxide, etc. and esters of the t-butyl perbutyl hydroperoxide polymerization initiator is dissolved benzoate type. The useful reducing components include in the monomeric mixture and eight percent (8%) of the compounds like the sulfites, bisulfites, hydrosulfites and monomeric charge (charge B) is then dispersed in the thiosulfites; ethyl and other alkyl sulfites; the sulfoxylates, charge A. The remaining 92% of the monomers (charge such as sodium formaldehyde sulfoxylate; and the like. B) is added to the reaction vessel by a conventional de- Especially preferred are initiator systems based on t-butyl layed addition technique over a period of 2 /2 hours. Durhydroperoxide and sodium formaldehyde sulfoxylate; and ing this time the temperature of the reaction batch is redox combinations such as mixtures of hydrogen permaintained in the range of from 41 to 45 C. while mainoxide and an iron salt; hydrogen peroxide and zinc formtaining mild agitation.

aldehyde sulfoxylate or other similar reducing agent; hy- The resulting latex has a total solids of 35.7%, a pH drogen peroxide and a titanous salt; potassium persulfate of 4.9 and a Brookfield viscosity of 23 centipoises. The and sodium bisulfate and a bromate mixed with a bipoly(vinyl acetate-dimethyl maleate-acrylic acid) resin sulfate. has a specific viscosity of 2.51 when measured as a 1% The use of equimolar amounts of initiator system comsolution in dimethyl sulfoxide at 25 C. Other properties ponents is generally preferred although the amount of of this latex are tabulated in Table 1 below.

each component as well as the total amount of catalyst EXAMPLES 2T0 10 used depends on the type of component used as well as on other polymerization conditions and may range be- The following Examples 2 to 10 are set forth to illustween .02 and 0.2% by weight of the total polymerizatrate variations in the latex polymerization reaction condition system, the preferred range being 0.02 to 0.06% for tions of the present invention. In each case the general the oxidizing component and 0.04 to 0.1 for the reducing procedures of Example 1 are followed except for the noted changes. The resulting latices have solids contents component.

The solids contents of the latices can be varied over in therange of from to 42% by weight and Brookfield a wide range. The preferred latices having a solids content viscositles 1n the range of from 10 to 50 cps. at 25 C.

in the range of from 15 to 65% by weight and mor pref- These examples are tabulated in the following Table 1.

TABLE I.SUMMARY OF EXAMPLES 1 TO 10 Example 1 2 3 4 5 6 7 8 9 10 iii'tfi. 62.03 57.7 57.87 62. 03 62.03 57. 70 62.03 57.03 52.03 57. 7o

Cha eB:

a otal monomer 35 40. 0 40.0 35- 0 35 0 40.0 35 4 35 40 Percent vinyl acetate.... 90 5 86.65 91. 65 90.5 86 5 90.5 90.5 80 5 90 5 90. 5 Percent dialkyl maleate 5 10.0 5. 0 5. 0 7 5 5. 0 5.0 5 0 5 0 5. 0 Percent acrylic acid 4 5 3. 35 3.35 4 5 6 0 4.5 4.5 5 5 4 5 4.5 Percent total coagulum. 0 68 0.02 0. 16 0 2 0 05 0.15 0.08 0 07 0 04 Pol er ro erties:

s geciiic giscosity 2.51 1. as 1.54 2. s1 2. 95 2. s5 2. 02 6.05 2.78 2.58

T l telon t iiff eg 'i nnflffi 3, 190/288 5,130 110 2, 350/380 2,000/283 2,150/320 3,320/370 3,560/423 3,040/360 1, 770/442 2, 030/310 1,530/430 2, 310/541 720/590 2, 000/574 1, 440/470 Dry, 80% an. 2340/3 3,200/350 erably from 35 to 55% by weight, based on the total In the foregoing Table 1, percent total coagulum refers weight of the latex. to all coagulum produced, both filterable and remaining During the polymerization reaction a conventional as foulmg on the impeller and wall of th rea to Thi base such as ammonium hydroxide or sodium hydroxide value is measured by recovering the coagulum by filtrais used to buffer the latex to a pH in the range of 4.0 tratlon and by scraping from the equipment, drying it,

to 6.0. weighing it, and calculating its percent weight based on The following examples are set forth in illustration of the calculated solids. Values in EXCESS 0f 0.75% indicate the present invention and should not be construed as a that Objectionable kettle fouling Would O c in Commer- 1i it i h fl U l otherwise i di t d, ll parts cial scale batches which would cause serious problems in product yields, product handling and equipment clean-up. Specific viscosity measurements are made on 1% solutions in dimethyl sulfoxide at 25 C.

and percentages given are by weight and polymerization temperatures are maintained in the range of from 41 to Tensile (p.s.i.) and elongation are measured according PART APREPA'R OF LATICES to ASTM Method D-882-67 after conditioning at 65 and 80% relative humidity. The wet values are obtained EXAMPLE 1 on 4 mil films which are immersed in water for five (5) A latex is prepared in conventional latex polymerizammutes Example 9 uses diethyl maleate as the dialkyl maleate component while all of the other examples use dimethyl maleate. Examples 1, 4, 5 and 7 to 9 use a phosphate ester tion equipment while maintaining a nitrogen atmosphere and mild agitation using the following charge:

Charge: Parts of an octyl phenol-ethylene oxide condensate (PEOPEO) A. while the other examples use a phosphate ester of a nonyl Water 62-03 phenol-ethylene oxide condensate (PENPEO). Example PEOPEO 1. 8 1 uses a single surfactant while Examples 2 to 10 use a Ammonium hydroxide (28%) 0.2 combination of a major amount of PEOPEO or PENPEO Sodium formaldehyde sulfoxylate 0.05 with a minor amount of sodium dihexyl sulfosuccinate t-Butyl hydroperoxide (90%) 0.03 (SDS) which is available commercially as AEROSOL B. MA. from American Cyanamid. Note in Examples 2 to Dimethyl maleate (DMM) 1.75 10 that when a combination of surfactants is used, the Vinyl acetate (VOAC) 3-1.67 percent total coagulum is significantly lower than in Ex- Acrylic acid 1-58 ample 1 wherein a single surfactant is used.

Examples 1 to 4 and 7 to 10 are prepared using ammonium hydroxide as the buffer agent while Examples 5 and 6 use sodium hydroxide. The high wet tensile strength of the polymers prepared in Examples 1 to 5 and 7 to 10 using ammonium hydroxide, indicate their suitability for use as a size in a water jet weaving process.

The polymeric products of Examples 2 and 3 contain only 3.35% acrylic acid monomer. These polymers have good water resistance, tensile and elongation making these polymers very suitable for use in water jet weaving processes using organic solvent desizing methods.

In order to be suitable for use as sizes in the water jet weaving process the polymeric size must have a good tensile strength, toughness and adhesion to the yarn under wet conditions. The specific viscosities of the polymers of the present invention are good indices as to wet tensile strength and toughness when considered in the context of the type and amount of comonomers present in the polymer. The preferred polymers of the present invention have a specific viscosity in the range of from 1.2 to 12.0 and more preferably in the range of from 1.3 to 10.0.

The correlation between specific viscosity of the polymers of the present invention and wet tensile strength are shown in the following Table 11 wherein five series of polymers are prepared using the general procedures of Examples 2 to 10 above. Variations in the amount of catalyst and polymerization temperatures lead to variations in the specific viscosity of the resulting polymers. These polymers are then tested for wet tensile strength and the results are tabulated in the following Table H.

TABLE IL-CORRELATION OF WET TENSILE STRENGTH WITH SPECIFIC VISCOSITY Polymer Wet tensile specific strength viscosity (p.s.i.)

1 Polymers are prepared using the following percent by weight monomer eharges A-vinyl acetate/dimethyl maleate/acrylic acid 91.65/5.0/3.37; B-vinyl acetate/dimethyl maleate/acrylic acid 90.5//4.5; C-vinyl acetate/dimethyl maleate/acrylic ac d 90/5/5; D-vinyl acetate/diethyl maleate/acrylic acid 90.5/5/4.5; E-vinyl acetate/dibutyl maleate/acrylic acid 91.65/5/3.35.

i Tensile values for 0-1 and 0-2 are determined at 80% RH.

The data in the foregoing Table II illustrate that in a given series, using the prescribed dimethyl maleate and diethyl maleate monomers of the present invention, the greater the specific viscosity the greater is the wet tensile strength. On the other hand, Series E prepared using dibutyl maleate has very low wet tensile strength as compared to comparable polymers having approximately the same specific viscosity. In this regard attention is directed to a comparison between Series E and Series A-3, A-4, B-1 and B-2.

EXAMPLES 11 TO 13 The following Examples 11 to 13 are set forth as control examples to illustrate the effect of polymerization temperature on the physical properties of the resulting latex. In each example the general charge and procedure of Example is repeated while the polymerization temperature is varied. The specific viscosity of the resulting 6 polymer is then measured. The results are tabulated in Table III below.

TABLE Ill-SUMMARY 0F EXAMPLES 11 TO 18 Polymerizetion Specific Example temp., C. viscosity 1 Run coagulated.

EXAMPLE 14 The general charge and procedure of Example 3 is repeated here except that fumaric acid is substituted for the acrylic acid used in Example 3. The reactants are mixed and heated. No significant polymerization reaction has taken place even after 24 hours.

EXAMPLE 15 Example 14 is repeated here except using crotonic acid in place of fumaric acid. The polymerization is carried out for 5% hours. At the end of this time, the reaction mixture is found to contain 9% by weight of free monomer based on the total latex weight. This low conversion rate makes the polymer process unacceptable for use on a commercial scale. Moreover, the polymer is found to have a specific viscosity of only 1.1 and is unacceptable for use as a size in a water jet weaving process.

EXAMPLE 16 In this example 88% by weight of vinyl acetate, 5% by weight of dimethyl maleate and 7% by weight of monoethyl maleate are interpolymerized according to the general procedure of Example 10.

The monomethyl maleate monomer is being used in place of the acrylic acid used in Example 10- The resulting polymer is found to have a specific viscosity of 1.8, Tensile Strength of 1800 p.s.i. dry and 1060 p.s.i. wet and elongation of 200% dry and 500% wet. The low wet tensile strength of this polymer coupled with poor wet adhesion to acetate fibers and film insolubility in aqueous alkali, makes it unacceptable for use as a size in a Water jet weaving process.

EXAMPLE 17 In this example dibutyl maleate is used in place of the dimethyl maleate and diethyl maleate used in Examples 1 to 10 above. The general polymerization procedures used in Example 1 are followed here using 91.65% by weight of vinyl acetate, 5.0% by weight of dibutyl maleate and 3.35% by weight of acrylic acid. The resulting polymer has a specific viscosity of 1.79, tensile strength of 2050 p.s.i. dry and 680 p.s.i. wet and elongation of 230% dry and 240% wet. The'low wet tensile strength of this polymer makes it unacceptable for use as a size in a water jet weaving process.

EXAMPLE 18 In this example methyl methacrylate is used in place of the dimethyl maleate used in Examples 1 to 8 and 10 above. The general polymerization methods of Example 4 are used here using a monomer charge of 89% by weight of vinyl acetate, 5% by weight of methyl methacrylate and 6% by weight of acrylic acid. The reaction mixture coagulated and no polymer was obtained for testing.

EXAMPLE 19 In this example acrylonitrile is used in place of the dimethyl maleate used in Examples 1 to 8 and 10 above. The general polymerization methods of Example 4 are followed using a monomer charge of 90% by weight of vinyl acetate, 5% by weight of acrylic acid.

After four hours reaction time only 6.5% monomers have been converted into polymer.

EXAMPLE 20 This example illustrates the criticality of using a surfactant which is a phosphate ester of an alkyl phenolethylene oxide condensate. Example 4 is repeated here except that octyl phenol-ethylene oxide condensate is used as the surfactant in place of the phosphate ester of octyl phenol-ethylene oxide condensate used in Example 4. The octyl phenol-ethylene oxide condensate used in this example is a well-known surfactant which is available commercially as Triton X-405 from Rohm and Haas. After three hours reaction time the batch was completely coagulated.

of the EXAMPLE 21 Example 20 is repeated here except using a surfactant which is a phosphate ester of an aliphatic alcohol-ethylene oxide condensate. After three hours reaction time the batch was completely coagulated.

PART B-TESTING OF THE LATICES OF EX- AMPLES 1 TO 5 AND 7 TO 10 AS TEXTILE SIZES The latices prepared in Examples 1 to 10 are tested in order to determine their suitability as yarn sizes in both conventional and water jet weaving processes. The sizes are prepared by dissolving the latex in an aqueous solution of base such as ammonia, ammonium carbonate, ammonium bicarbonate, sodium hydroxide or sodium carbonate. Other basic solutions may be used to dissolve the latices as for example, aqueous solutions of alkali metal hydroxides, carbonates and bicarbonates as well as aqueous solutions of methylamine, dimethylamine, trimethylamine, ethylarnine, diethylamine, triethylamine, npropyl amine, n-butyl amine, morpholine, etc. The sizing solutions contain between 1 and 25 percent solids. The concentration is readily selected by one skilled in the art so that the desired ad-on to the yarns and solution viscosity for ease of application of the sizing solution are obtained.

The key properties cosidered in these tests are listed below:

Solubility--all of the latices in question are soluble in aqueous bases such as aqueous ammonium hydroxide to provide sizing solutions.

Sizing Solutionsprepared from the latices of Examples 1 to 5 and 7 to 10 have Brookfield viscosities in the range of from 1 to 300 centipoises at 4 to 5% solids allowing ease of application of the yarn.

Wet Tensile Strength-films prepared from the latices of the present invention have wet tensile strength in excess of 1000 p.s.i. and the necessary toughness and film integrity required in water jet sizes.

Percent Elongationthese values further indicate that the latices in question have the necessary film toughness required in water jet sizes.

Adhesionthe latices of Examples 1 to 5 and 7 to 10 have been tested and found to have good adhesion to the following yarns-filaments, acetate, polyester, rayon, texturized polyester, nylon; spun polyester, cotton, rayon and wool; acetate, nylon and blends thereof.

Resolubility in mild alkali-dried films 0f the latices in question are readily soluble in tetrasodium pyrophosphate-surfactant solutions which indicates that the size is easily removed from the woven fabric. The size is also soluble in chlorinated solvents used in desizing operations.

Size eificiencyis a measure of the amount of size add-on required in a given operation. The add-on is the amount of size that must be applied to the yarn in order to permit it to be woven on a water jet loom. In general, the less size add-on required, the more efiicient the size. Sizes prepared from the latices of the present invention have excellent efiiciency as is indicated by the following 22 to 24.

EXAMPLE 22 A latex composition is prepared as in Example 10 above using monomeric charge of 90.5% by weight of vinyl acetate, 5% by weight of dimethyl maleate and 4.5 by weight of acrylic acid. The resulting latex, wherein the polymer component has a specific viscosity of 2.7, is dissolved in aqueous ammonium hydroxide to give a 5.0% solids solution having a pH of 9.0.

This sizing solution at F. is applied to a 150 denier, 41 monofilament, low twist bright acetate yarn on a commercial eleven can slasher at a rate of 90 yards per minute for a size add-on of 2.1%. Drying can temperatures on the slasher are l85/200/200/215/220/220/230/ 220/210/80/ F. respectively. The split is very easy, and no ends break out at start-up.

The sized warp is entered into a Nissan Prince water jet loom, where at 400 picks per minute the weaving operation runs at very high efiiciency, 98%) with no second quality fabric produced. The woven fabric has a dry appearance in contrast to warps woven with lower M.W. (specific viscosity of 0.7) materials which become wet" and slimy. Successive warps shows the same excellent performance. This fabric was desized in a conventional process by scouring in tetrasodium pyrophosphate wetting agent baths. The size is also removable in a chlorinated solvent scouring process.

EXAMPLE 23 Example 22 is repeated here using a latex with a specific viscosity of 2.73. This latex is dissolved with aqueous ammonium hydroxide to give a 4.5% solids solution having a pH of 9.2. The size is applied to a 75 denier 20 monofilament low twist (75/20/LT) bright acetate yarn on a seven can slasher. The slasher is run at 25 yards per minute at a size add-on of 1.9% using drying can temperatures of 210/ 160/ /150/ cold, respectively. The warp splits very easily and weaves at very high efiiciency to give good quality fabric which is desized as in Example 22.

EXAMPLE 24 This example is set forth to illustrate the exceptional efiiciency of the sizes prepared according to the processes of the present invention. Example 22 is repeated here using a latex with a specific viscosity of 2.73. This latex is dissolved with aqueous ammonium hydroxide to give a 4.5% solids solution having a pH of 9.2. This size is applied to a 150 denier 40 monofilament, 0.8 twist (150/ 40/0.8) bright acetate yarn on a seven can slasher at 55 yards per minute at a size add-on of 1.6%. Drying can temperatures are 190/210/210/2l0/l90/cool. The warp splits very easy, and no ends break out during the sizing operation. The warp weaves at very high elficiency to give good quality fabric which is desized as in Example 22. The add-on rate (1.6%) used in this example is unusually low when compared to the sizes of the prior art which must be used in much larger amounts.

Sizes which are obtained from polymers prepared by the processes of the present invention are compared to commercially available textile sizes. The results of these comparisons is set forth below. In these tests the toughness value is the product of tensile times elongation,

Various sizes in the form of ammonium salts are applied to acetate and polyester filaments under water jet conditions. The size is tested for wet tensile, wet elongation, wet toughness and wet adhesion. The results are tabulated in the following Table IV.

TABLE IV.TESTS N WATER JET SIZE 0N ACETATE AND POLYESTER FILAMENT Percent Tou h- Adh si 1 Specific Tensile elongamiss 6 on Composition viscosity (p.s.i.) tion (X Acetate Polyester VA/DMM/AA 90.5/5/4.5 2 36 2150 540 116 G d. VA/DBM/AA, 91.65/5/3.35 1 79 700 250 17.5 P r. VA/CA 96/4 0 7 750 200 Good VA 1 4 700 400 28 Poor. 1 9 60 540 3. 2 Do.

:.-.: O D0. 480 200 9.6 Excellent.

1 Values are weight percent. VA=vinyl acetatezDMM=dimethylmaleate:DBM=dibutyhnaleate:MMM= monomethyl maleate: MIBM =monoisobutyl maleate: AA=acrylic acid: MA =maleic anhydride: AE =acrylate ester.

i Qualitative adhesion tests are run under wet conditions on fiber imbedded into size.

Size A is obtained from a latex that is prepared according to the processes of the present invention. Sizes C to G are commercially available sizes which are representative of the prior art. Note that Size A has good to excellent adhesion and is at least five times (5 X) tougher than the sizes of the prior art.

CONVENTIONAL SIZE ON ACETATE, RAYON AND TEXTURIZED POLYESTER Various sizes in the form of sodium salts are applied to filament acetate, rayon filament and texturized polyester. The sizes are then tested under conditions of 65% RH. for tensile, elongation, toughness and adhesion. The results are tabulated in the following Table V.

1 Compositions A to F are the same as in Table IV above except that; A has a specific viscosity of 2.94: G is a commercial gelatin size: H is an equimolar styrene-maleic anhydride copolymer.

3 Numerical values are pounds required to break 56 x M inch lap joints.

TABLE VI.-LOOM FINISH ACETATE AND NYLON SIZES Percent Tough- Adhesion (lbs.) Tensile elonness (X10 Acetate (p.s.i.) gation Nylon 3,450 370 128 19 13 2,060 230 47 40 9 1,660 130 22 27 11 2,250 160 14 16 E0 3,830 20 8 14 11 Polyvinylalcohol. 2,000 500 100 15 1 Compositions A to E same as in Table IV above except that A has a specific viscosity of 2.66. The polyvinyl alcohol used is a partially hydrolyzed low molecular weight polymer which cannot be used as a loom finish because of its water sensitivity.

2 Tested as in Table V.

Once again, Size A, which is representative of the sizes of the present invention, shows superior toughness. The adhesion of this size to acetate and nylon further indicate its utility as a textile size.

SPUN SIZES FOR AQUEOUS REMOVABLE AND SOLVENT REMOVABLE APPLICATIONS In certain applications it is desirable to size yarns such cotton, rayon, wool, polyester and blends thereof and then remove the size from the resulting fabric using either aqueous alkali or an organic solvent. In the following tests various sizes are applied to polyester and then tested under conditions of 80% RH. for tensile, elongation, toughness, adhesion and solubility. The test results are tabulated in the following Table VII.

TABLE VIL-SPUN SIZES FOR AQUEOUS REMOVSABLE AND SOLVENT REMOVABLE APPLICATION Percent Tongh- Solubility Tensile elonness Adhesion (p.s.i.) gation (X10 (p.s.i.) Aqueous Organic Size;

650 620 40 4,800 420 190 6,600 320 210 OMS/binder- 2, 800 17 Starch/Binder 2,700 30 8 1 Compositions A to E same as in Table IV above except that A has a specific viscosity of 3.71 and aVA/DMM/AA composition of 90/5/5% by weight. PVOH-PH is a high molecular weight partially hydrolyzed polyvinyl alcohol: PVOH-FH is a high molecular weight fully hydrolyzed polyvinyl alcohol: CMC/binder is a blend of carboxymethyl cellulose and an acrylate binder: Starch/binder is a blend of starch and an acrylate binder.

1 Adhesion tests are run oi a $6 square inch polyester to wood board bond.

8 The aqueous solution contains a tetrasodlurn pyrophosphate-wetting agent combination. The organic solvent used is trichloroethylene.

Size A, which is obtained from a latex prepared according to the processes of the present invention, exhibits greater toughness and better adhesion than the sizes of the prior art.

LOOM FINISH ACETATE AND NYLON SIZES Various sizes in the form of ammonium salts are applied to acetate and nylon filament yarns. In the acetate application the size remains on the resulting fabric as a Size A which is representative of the sizes of the present invention exhibits excellent toughness and adhesion. Moreover, this material is removable in conventional aqueous desizing operations as well as in organic solvent desizing operations. This latter feature is especially important where water shortages or water pollution problems exist.

Another feature of the present invention is the fact that the polymeric material may be dissolved in organic solvents to form a size. This feature is especially desirable in certain applications wherein solvent size removal techniques are also employed. In such applications the polymer solids are recovered from the latex, using conventional means. The polymer solids are then dissolved in an organic solvent to form the textile size and the size in the form of an organic solvent solution is applied. Size removal may be accomplished using aqueous alkali or organic solvent methods.

Preferred organic solvents used in preparing the sizes are alcohols, ketones, esters and aromatic solvents. Especially preferred are chlorinated aliphatic hydrocarbons such as methylene chloride, methylene bromide, chloroform, bromoform, ethylene dichloride, ethylene dibromide, ethylidene chloride, ethylidene bromide, s-tetrachloroethane, hexachloroethane, s-dichloroethylene, 1,1- trichloroethane, 1,1,2-trichloroethane, trichloroethylene, trimethylene bromide, trichlorobromoethane, trichloromethane, 1,2,3-trichloropropane, 1,1,2-trichloropropane, trifluoro-1,2-tribromoethane, trifiuoro 1,1,2 tribromoethane, trifiuoro-l,1,2-trichloroethane, 2,2-dichloro-1- bromoethane, 1,3-dichloro 2 methyl-propane, 1,2-dichloro-2-methylpropane, 1,1-diiodoethane and the like. Chlorinated aliphatic liquid hydrocarbons are preferred in the practice of this invention because of their generally lower cost, greater availability and the ease with which these solvents may be handled.

From the foregoing, it should be obvious that many variations are possible in the present invention without departing from the spirit and scope thereof. Conventional adjuvants, lubricants, defoamers and plasticizers may be added without departing from the scope of the invention.

What is claimed is:

1. A composition for sizing textile yarns comprising a solution of a latex interpolymerization product of from 83 to 95% by weight of vinyl acetate, from 2 to 10% by weight of a dialkyl maleate selected from the group consisting of dimethyl maleate and diethyl maleate and from 3 to 7% by weight of acrylic acid based on the total weight of the monomers, in an aqueous base.

2. The composition of claim 1, wherein the amount of vinyl acetate is in the range of from 87.5 to 91%, the amount of dialkyl maleate is in the range of from to 7.5% by weight and the amount of acrylic acid is in the range of from 4 to 5% by weight.

3. The composition of claim 1, wherein the dialkyl maleate is dimethyl maleate.

4. The composition of claim 1, wherein the interpolymer has a specific viscosity when measured as a- 1% solution in dimethylsulfoxide at C. in the range of from 1.2 to 12. I I

5. The composition of claim 1, wherein the tains from 1 to by weight of interpolymer based on the total weight of the aqueous solution.

6. The composition of claim 1, wherein the base is selected from the group consisting of alkali metal hy, droxides, carbonates and bicarbonates, ammonia, am"- monium carbonate, ammonium bicarbonate, methylamine, dimethylamine, trimethylamine, ethylamine,' diethylamine, triethylamine, n-propylamine, n-butylamine and morpholine. i

7. A composition for sizing textile yarns comprising a solution in aqueous base, of the interpolymerizati on product of from 87.5 to 91% by weight of vinyl acetate, from 5 to 7.5 by weight of dimethyl maleate and from 4 to 6% by weight of acrylic acid based on the total weight of the monomers; wherein the interpolymer has a specific viscosity when measured as a 1% solution in dimethylsulfoxide at 20 C. in the range of from 1.2 to 12; and wherein the size contains from 1 to 25% by weight of interpolymer based on the total weight of the aqueous solution.

References Cited UNITED STATES PATENTS 3,057,812 10/ 1962 Straughan etal. 260-29.6 TA

3,231,534 1/1966 Blades et al. 260-296 TA 3,449,282 6/1969 Lasher et a1. 260-296 TA 3,723,381 3/1973 Corey et al. 260-33.8 UA

3,759,858 9/1973 Corey et al. 260-29.6 TA

LUCILLE M. PHYNES, Primary Examiner US. Cl. X.R.

1l7-138.8 R, 139.5 A, 161 UT; 260-296 HN and N,

78.5 B, UA and E size con- 

